Patent GB-602170-A (GB)
Title: Manufacture of new azo-dyestuffs
IPC: C09B43/16
Filed: 1944-11-16
Abstract: 1 - Amino - 4 - aroylaminobenzene - 2 - carboxylic acids are obtainable by treating 1-formylamino - 4 - aminobenzene - 2 - carboxylic acid with an aroyl halide (e.g. benzoyl, 4-chlorobenzoyl or 3-methoxybenzoyl chloride, benzoyl chloride-3-sulphonic acid or naphthoic acid chloride), and then saponifying the formylamino group.ALSO:Stilbene-azo dyestuffs of the general formula <FORM:0602170/IV (c)/1> wherein R1 represents the residue of a compound containing an enolizable keto group, A represents an aromatic nucleus of the benzene series in which the -N = N- and -NH- groups are in p-position to one another and which contains in o-position to the -N = N- group a carboxyl or hydroxyl group as a group capable in conjunction with the grouping -N = N-R1 of leading to the formation of complex metal compounds, R2 represents an aromatic residue which contains in o-position to the -N = N- group a group likewise capable in conjunction with the grouping -N = N-Py of leading to the formation of complex metal compounds, Py represents the pyrazolone residue of a 1-aryl-5-pyrazolone, and x represents a connecting member derived from a heterocyclic compound having at least two exchangeable halogen atoms, such as cyanuric chloride, are manufactured by (1) condensing together equimolecular proportions of a heterocyclic compound containing at least two exchangeable halogen atoms, such as cyanuric chloride, an aminoazo dyestuff R1-N = N-A-NH2 and an aminoazo dyestuff <FORM:0602170/IV (c)/2> or (2) coupling a pyrazolone derivative <FORM:0602170/IV (c)/3> with a diazotized amine R2NH2, then diazotizing and coupling with a compound having an enolizable keto group, or (3) coupling a dyestuff with a diazotized amine R2NH2. The products <FORM:0602170/IV (c)/4> may be converted into complex metal (e.g. cobalt, nickel, iron, chromium and especially copper) compounds during manufacture, in substance or on the fibre (especially natural or regenerated cellulose fibres or materials containing them, e.g. mixtures of cotton or wool with artificial fibres of regenerated cellulose or regenerated cellulose given a matt effect by means of inorganic pigments).  Mixtures of wool and viscose staple fibre may be dyed in a neutral bath in the presence of sodium or potassium chromates.  In examples: (1) 411-aminostilbene-21 : 211-disulphonic acid -41-(3-methyl-5-pyrazolone) is condensed with cyanuric chloride in the presence of sodium carbonate and the product is warmed with 4-(41-amino-21-carboxy) -phenylazo-3-methyl-5-pyrazolone in the presence of caustic soda solution and then with aniline in the presence of sodium bicarbonate and carbonate, after which the product is coupled with diazotized 4-benzoylamino-1-aminobenzene-2-carboxylic acid (or this coupling may precede the initial condensation with cyanuric chloride); (2) in the latter alternative in (1), the 4-benzoylamino-1-aminobenzene-2-carboxylic acid is replaced by 1-amino-2-hydroxy-4-nitrobenzene, 1-amino-2-hydroxy-3 : 5 : 6 - trichlorobenzene or 1 - amino - 2 - hydroxy-3 (or -5) -nitro-5 (or -3) -chlorobenzene, or (3) by 1-amino-4-bromobenzene-2-carboxylic acid; in this case the cyanuric chloride may be replaced by 2 : 4-dichloroquinazoline, the condensation with aniline then being omitted; (4) in the first of the alternative processes of (1), the 4 - benzoylamino - 1 - aminobenzene - 2 - carboxylic acid is replaced by 4-nitro-6-chloro-, 3 : 4 : 6-trichloro- or 4- or 5-nitro-2-aminophenol; (5) in the second of the alternative processes of (1), the aminoazo dyestuff in the second stage of the condensation with cyanuric chloride is replaced by its 1-(211-chloro-511-sulpho)-phenyl derivative; (6) the initial condensation product in the first alternative process of (1) is further condensed with 1-amino-4-nitrobenzene-5-carboxylic acid and with aniline, the nitro group is reduced by means of sodium sulphide and the product is coupled with diazotized 1-amino-4-benzoylaminobenzene-2-carboxylic acid and then diazotized and coupled with 3-methyl-5-pyrazolone; (7) in the process of (5), the aminoazo dyestuff in the second stage is replaced by one containing a hydroxy instead of a carboxyl group in the 21-position (obtained by coupling diazotized 1-amino-2-hydroxy-4-nitrobenzone with 1-(21-chloro-51-sulpho) - phenyl - 3 - methyl - 5 - pyrazolone and reducing the nitro group); (8) cotton is dyed with the product of (1) from a bath containing sodium carbonate and sulphate, and after-treated in the same bath with a solution of copper sulphate and tartaric acid neutralized with caustic soda, yielding a yellow dyeing.  Other components specified are: compounds having enolizable keto groups, corresponding to the residue R1: acetoacetic acid derivatives (e.g. arylides), pyrazolones obtained by the condensation of hydrazines with acetoacetic ester (e.g. 1-phenyl-3-methyl-5-pyrazolone or its derivatives substituted in the benzene nucleus) or with other b -ketocarboxylic esters (e.g. oxalacetic ester), derivatives of malonic acid, barbituric acid and its derivatives, benzoylacetone and 2 : 4-dihydroxyquinoline; heterocyclic compounds corresponding to the residue x: cyanuric bromide, 2-phenyl- and 2-methyl-4 : 6-dichloro-1 : 3 : 5-triazine and 2 : 4 : 6-tribromopyrimidine; the third halogen (if present) in the foregoing may be replaced by reaction with ammonia, primary amines (e.g. monomethylamine, monoethanolamine or 1-amino-4-hydroxybenzene-3-carboxylic acid) or secondary amines (e.g. monomethylaniline); amines R2NH2 : 2-aminophenol and its 4-chloro-, 4 : 6-dinitro-, 5-nitro-6-chloro- and 4-methyl-derivatives, 4- (or 6)-nitro-2-aminophenol-6 (or -4)-sulphonic acid, 2-aminophenol-4 - sulphonamide, 2 : 1 - aminonaphthol - 4 : 8 - disulphonic acid, 1 : 2-aminonaphthol-4-sulphonic acid, 1 - amino - 6 - nitro - 2 - naphthol - 4 - sulphonic acid, and 1-aminobenzene-2-carboxylic acid and its 4-chloro-, 4-nitro- and especially 4-aroylamino-derivatives.